Aqueous dispersion of glass fibers and method and composition for producing same

ABSTRACT

A uniform, stable low foam aqueous dispersion of glass fibers can be accomplished with the present invention. This accomplishment is obtained by the use of a unique combination of an alkyl sulfate quaternary salt of an alkyl amino fatty amine or amide and a water dispersible, liquid mineral oil, inorganic silica defoaming agent. The blend of the dispersing agent and the defoaming agent can be present on the glass fibers to be dispersed in the liquid solution or can be added to the aqueous solution prior to the addition of the glass fibers.

This is a division of application Ser. No. 221,741, filed Dec. 31, 1980.

The present invention is directed to a stable, low foam, uniformdispersion of glass fibers and strands in water, method of making same,sizing composition for treating the glass fibers, and the sized glassfibers and strands for use in producing glass fiber paper.

Glass fibers have been used in combination with other types of fibers oralone in the production of paper-like sheet materials. Glass fibers havebeen used a supplemental fiber in specialty, synthetic, fiberwood, pulp,composite papers. It has also been recognized that small diameter glassfibers can be used to produce paper-like material that has a highstrength and can be used as air or liquid filtration paper. With thegrowing concern of possible health hazards associated with asbestosfibers, the use of glass fibers as a replacement for asbestos fibers inproducing sheet-like material is being investigated.

One problem that must be solved to enable glass fibers to replaceasbestos fibers in paper-like products and others is that glass fibersare more difficult to disperse in water and they do not fibrillate inthe usual paper-making sense. The dispersion problem occurs when aslush, an aqueous suspension of dispersed fibers, of the glass fibers orthe combination of glass fibers and cellulose fibers is prepared as apreliminary step to the formation of a wet web. The dispersion problemof glass fibers is caused by several factors including the length of thefibers, the electrical charges on the fibers, the diameter of thefibers, differing water absorbtion characteristics of the fibers, andthe presence of textile sizes or finishes on the glass fibers. When theglass fibers have small diameters, i.e., a micro fiber with a diameterup to around 6.4 microns, the glass fibers produced either without asizing composition, or with a sizing composition that can be easilyremoved, or with a sizing composition containing a water-dispersiblestarch binder have found some utility. When the diameter of the glassfibers increases above the micro size the problem of poor waterdispersibility becomes increasingly significant.

The art of trying to improve the dispersibility of glass fibers hasemployed the use of additional chemicals that may be anionic, cationicor nonionic depending upon the nature of the fiber. The chemicals may besupplied as a finish on the fiber or added separately to the aqueoussystem. For example, the art discovered that an acid pH obtained by theaddition of strong mineral acids or sodium hexametaphosphate was usefulin dispersing glass fibers (U.S. Pat. No. 3,749,638 and U.S. Pat. No.2,919,221). Also the art has shown that polyacids, like phosphoric, andcarboxy methyl cellulose, can be used as dispersing aids (U.S. Pat. No.2,802,734). In addition, the art has shown that linear polysiloxanescontaining at least 6 silicon atoms with each atom having 2non-hydrolyzable oleophilic groups can be used to disperse glass fibers(U.S. Pat. No. 4,052,256). The use of these additional chemical agentseither in a sizing composition for the glass fibers or as additionalagents added to the aqueous system may be useful in dispersing microsize glass fibers and some may be useful in dispersing larger diameterglass fibers.

These is still a need in the art for a sizing composition for glassfibers that renders the protection needed for the glass fibers infurther processing while at the same time that does not interfere withbut actually assists in dispersing glass fibers in an aqueous solution.This need must be fulfilled without the creation of additional problems.There is also a need in the art for chemical agents that can be added towater to improve the dispensibility or inhibit agglomeration of glassfibers in aqueous solutions, without creating additional problems. Onesuch problem that is created in producing aqueous dispersions of glassfibers, when additional additives are added to the water or present inthe size residue on the glass, is the foaming of the resultant aqueousdispersion of glass fibers. Some agents added to the aqueous solution toassist in dispersing the glass fibers cause an intolerable amount offoaming of the aqueous dispersion. Such foaming of an aqueous dispersioncontaining glass fibers would make the dispersion unacceptable for useas a slush in papermaking.

It is an object of the present invention to provide a sizing compositionfor glass fibers that yields sized glass fibers with improved waterdispersibility.

It is a further object of the present invention to provide glass fibershaving a sizing composition for use in preparing a stable, low foamaqueous dispersion for use in the production of glass fiber-containingpapers.

It is another further object of the present invention to provide astable uniform, low foam, aqueous dispersion of chopped glass fibers,particularly glass fibers with larger diameters and lengths, for use asa slush in the production of glass fiber-containing papers.

It is an additional further object of the present invention to provide amethod of making a stable, low foam aqueous dispersion containingchopped glass fibers having large diameters and/or long lengths, wherethe aqueous dispersion is useful in papermaking.

SUMMARY OF THE INVENTION

The aforementioned objects of the present invention are achieved byproviding an aqueous dispersion of chopped, glass fibers having presenta nitrogen-containing fatty acid derivative and a water-dispersible,liquid, mineral oil, and inorganic silica type defoaming agent. Thenitrogen-containing fatty acid derivative is selected from fatty acidsof alkyl amino sulfonic acids. The water dispersible, liquid defoamingagent is selected from those mineral oil, and inorganic silica typedefoaming agents that are compatible with the nitrogen-containing fattyacid derivatives which act as a dispersing agent. The amount of thedispersing agent and the amount of the defoaming agent present toproduce the aqueous dispersion of chopped glass fibers depends upon themanner in which the dispersant and defoaming agent are used. Thedispersant and defoaming agent may be added to an aqueous solutionbefore the addition of the glass fibers, or the dispersant and defoamercan be incorporated into an aqueous sizing composition for treatingglass fibers to be added to the aqueous solution.

The treated glass fibers prepared by the application of an aqueoustreating composition having at least the dispersant and defoaming agentduring the formation of the glass fibers also forms an aspect of thepresent invention. In addition, another aspect of the present inventionis the blend of the dispersant and defoaming agent that is to be addedto the aqueous solution before the glass fibers to produce the low foamaqueous dispersion of glass fibers.

The present invention also embodies a method for dispersing glass fibersin an aqueous solution wherein an amount of about 50 to about 300 partsper million (PPM) of a blend of 50 to 95 weight percent of thedispersing agent and about 5 to about 50 weight percent of the defoamingagent are added to the desired amount of water. The addition isaccomplished with the use of agitation. Chopped glass fiber strandseither sized or unsized are added to the aqueous solution with agitationin an amount of around one half weight percent of one half inch choppedglass fiber strands or any equivalent amount of chopped glass fiberstrands of different dimension. The addition of the glass fibers isaccomplished with the use of agitation to produce the aqueous dispersionsystem of glass fiber strands for use in papermaking.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an Infrared (IR) spectrum of the blend of diethyl sulfatequaternary of an alkyl amino oleylamide dispersant and a mineral andinorganic silica preferably colloidal silica surfactant mixture used asa defoaming agent.

FIG. 2 shows an IR spectrum of the mineral oil and inorganic, preferablycolloid silica-surfactant defoaming agent mixture.

Both IR spectrums were produced in a Perkin-Elmer IR machine from asmear of the material on a salt plate.

DETAILED DESCRIPTION OF THE INVENTION

As previously discussed, the problem with producing aqueous solutionshaving glass fiber strands is mainly the difficulty in achieving auniform distribution with the chopped glass fiber strands in the aqueoussolution. As previously described, the art has used numerous approachesto overcome this problem. In trying to overcome this problem, oneadditional problem that has been observed is some incompatibilitybetween the dispersing agent, defoaming agent and glass fibers. Whensome dispersing agents work well in dispersing glass fibers in anaqueous solution, the addition of some defoaming agent to the mixturemay cause the glass fibers to percipitate or settle out. This is thecase even when some of the defoaming agents are compatible with thedispersing agent.

I have found that when a particular type of dispersing agent is used incombination with a particular type of defoaming agent and used in waterwith the chopped glass fibers, an aqueous dispersion of glass fibers isproduced where the dispersion has good uniformity of the glass fibers inthe aqueous solution and low foam. This aqueous dispersion of glassfibers is achieved without the problem of excess foam and without theproblem of a defoaming agent ruining the dispersion of the glass fibersin the aqueous solution.

The glass fibers useful in producing the aqueous dispersion of thepresent invention are any conventional glass fibers having filamentdiameters from the micro size to the macro size.

The glass fiber strands themselves are composed of glass fibers producedfrom molten streams of glass attenuated from small orifices in a bushingin a glass batch melting furnace. The glass fibers are obtained fromconventional "E-Glass" and/or "621-Glass" and derivatives thereofincluding any more environmentally acceptable derivatives. The glassfiber strands may be produced in a wet chop or dry chop operation toproduce chopped glass fiber strands having lengths particularly fromaround 1/32 inch to around 2 inches. Generally the glass fibers makingup the dry or wet chopped glass fiber strands have filament diametersranging from about 5 to about 27 microns. The chopped glass fiberstrands can be of a filament diameter in this range or can be a mixtureof filament diameters having an average filament diameter in this range.Representative of a method of fiber formation and sizing application isthe process illustrated in FIG. 1 of U.S. Pat. No. 3,025,588.

Generally, such an application involves having glass fibers emerge fromorifices of an electrically heated bushing of a glass batch meltingfurnace. These fibers are attenuated and by means of a strand pullingdevice these filaments are gathered to form a strand of glass fiberswhich may comprise numerous individual fibers. The sizing is applied tothe fibers by a conventional size applicator, such as a kiss applicatoror a belt applicator device (although spray type applicators could beused). Detail of a sizing applicator is shown in U.S. Pat. No.2,728,972. The filaments after exiting the bushing are cooled by air orpreferably water. The filaments are gathered into bundles by a gatheringshoe and are then led to a strand pulling device such as illustrated inU.S. Pat. No. 3,292,013. The glass fiber strand or strands, if thefilaments exiting from the bushing have been separated into severalstrands, are then wound onto a forming tube on a collet rotating atapproximately 7,500 rpm to produce a strand travel of approximately12,000 to 15,000 feet per minute. The glass fiber strand formingpackages are then dried and the strands from the package may be drychopped separately or together or in the form of roving.

The wet chop operation for producing chopped glass fibers having anaqueous sizing or treating composition can be performed by anyconventional wet chop process known in the art. For example theprocesses of U.S. Pat. Nos. 3,869,268; 3,996,032; 4,043,779; 4,045,196;and 4,158,555; can be used.

When the glass fiber strands are composed of filaments having a diameterlarger than around 13 microns, the blend of the dispersing agent anddefoaming agent that is used in the aqueous sizing composition need notbe accompanied by any other components other than water. When the glassfiber strands are composed of filaments having a diameter smaller thanaround 13 microns, the dispersing agent and defoaming agent present in asizing composition should also be accompanied by a film former and/orlubricant and water. An additional ingredient that might also be presentin any sizing composition having the dispersing agent and the defoamingagent blend is a silane coupling agent. Any of the conventional filmformers, lubricants, and silane coupling agents can be used in thesizing composition in conventional amounts.

The dispersing agent that can be used in a sizing composition fortreating the glass fibers or can be used by the addition to an aqueoussolution before the addition of the glass fibers to the aqueous solutionis of the type known as dialkyl sulfate quaternary of an alkyl aminofatty amine or amide. This nitrogen-containing fatty acid derivative canbe a mixture of compounds form this chemical type. The fatty acid amineor fatty acid amide used to produce the quaternary ammonium saltgenerally contains at least 8 carbon atoms and preferably at least 14carbon atoms. Nonexclusive examples of the fatty acid amine or fattyacid amide include: odecyl, n-tetradecyl, n-hexadecyl, lauryl, myristyl,palmityl, oleyl, coconut oil, tallow oil, hydrogenated tallow oil,cotton seed oil, dilauryl oil, dimyristyl, dipalmityl, distearyl,dicoconut oil, dihydrogenated tallow oil, and soya oil. In the dialkylportion of the quaternary ammonium salt examples of unsubstitutedhydrocarbon radicals that can be used within that grouping includemethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. Aparticularly useful quaternary ammonium salt is the diethyl sulfatequaternary of an alkyl amino oleylamide avaiable from Diamond ShamrockCompany under the trade designation "Nopco, 2173 B" material. Thesenitrogen-containing fatty acid derivatives can be produced by anyconventional process known to those skilled in the art, such as,reaction of the fatty acid to produce the fatty acid derivative, theamine, or amide, and the reaction of this compound with dimethyl sulfateto produce the quaternary ammonium ethyl sulfate or the reaction of thefatty acid amine or amide with the sulfur-containing compound likeN-methyl taurine. It is also within the scope of the present inventionto use this type of dispersing agent in combination with other types ofdispersing agents such as the trialkylarylalkyl ammonium halides,wherein the predominant amount of the dispersing agent is thenitrogen-containing fatty acid derivative and the minor amount is thehalide dispersing agent.

The defoaming agent useful in the present invention is a waterdispersible, liquid, mineral oil, inorganic silica type defoaming agent,where the mineral oil is the predominant component. Preferably themineral oil inorganic silica defoaming agent has colloidal silica andhas a low silicone content of around less than 0.5 percent. In thedefoaming agent mixture of mineral oil and colloidal silica, anysurfactant such as cationic, anionic, nonionic or amphoteric can be usedto make the mixture water dispersible. Preferably a nonionic surfactantis used. Particularly useful defoaming agents are the defoamersavailable from Diamond Shamrock Chemical Company, Nopco ChemicalDivision, under the trade designations "319R" and "319M". The 319Rdefoamer has an IR spectrum of FIG. 2 and a amber liquid appearance,silicon content of less than 0.2 percent, 100 percent activity, 7.1 pHfor 2% solution at 25° C., and is damaged upon freezing. The "319M"defoamer has an amber liquid appearance, silicone content of less than0.5 percent, 100 percent activity, 6.6 pH of 2% solution at 25° C., andis damaged on freezing.

The dispersing agent and defoaming agent are used in a blend where theamounts of the dispersing agent in the blend are in the range of about50 to about 95, preferably about 75 to about 95, weight percent of theblend and the amount of the defoaming agent is in the range of about 5to about 50, preferably about 5 to about 25, weight percent of theblend. The blend of the Nopco 2173B nitrogen-containing fatty acidderivative and the Nopco 319R defoaming agent has an IR spectrum asshown in FIG. 1. This blend can be used in a sizing composition to treatthe glass fibers, wherein the other components in the sizing compositiondepend upon the particular filament diameter of the glass fibers makingup the glass fiber strand. When the blend is used in a sizingcomposition the amount of the blend used is in the range of about 0.1 toabout 50, preferably 0.5 to 20, weight percent of the aqueouscomposition. In the case of larger diameter fibers, the blend is theonly component present in addition to water, but a silane coupling agentmay also be incorporated into the aqueous sizing composition inconventional amounts. When the filaments are of a smaller diameter theblend is accompanied in the sizing composition with a film former and/orlubricant and/or silane coupling agent. When chopped, treated glassfiber strands are produced by the wet chop process and the filamentdiameter of the fibers is over around 13 microns, the aqueouscomposition has the blend, a conventional film former like anyconventional starch including cationic starches, lubricant, cationiclubricant, and optionally a silane coupling agent. When chopped, treatedglass fiber strands are produced by a dry chop process the aqueoustreating composition has the blend, a film former, nonionic lubricant,silane coupling agent, and around half as much cationic lubricant asused in the wet chop process. The amounts of the components other thanthe blend in the composition are conventional amounts known in the art.With all the components in the aqueous treating composition the totalsolids of the composition is about 5 to about 50 weight percent.

The blend may also be used as an additive to the aqueous solution beforethe glass fibers are added to the aqueous solution to form thedispersion. In this instance the amount of the blend used is in therange of of about 50 to about 300 parts per million (PPM) of the aqueoussolution, although greater amounts may be used but diminishing returnsare obtained as far as further improvement in the dispersion. Aparticularly useful blend has the IR spectrum of FIG. 1 and has 98.31percent solids, pH of 6.3 for 10% solids solution, and a viscosity of13800.0 cps #6 spin at 50 RPM.

In addition to the blend in the aqueous sizing composition or as anadditive to the aqueous solution, a viscosity building agent may beused. Non-exclusive examples of viscosity building agents includecarboxy methyl cellulose and soluble salts thereof, carboxy methylhydroxy ethyl cellulose and soluble salts thereof and hydroxy ethylcellulose and mixtures thereof. Particularly useful viscosity buildingagents are available from Hercules, Inc. under the trade designationNatrasol 250 LR and HR substituted and unsubstituted hydroxy ethylcellulose.

When the blend of the dispersing agent and defoaming agent are used inan aqueous sizing composition, the sizing composition with or withoutadditional components is prepared by conventional methods known to thoseskilled in the art. The sizing composition is applied to the glassfibers, while they are being formed by conventional methods known tothose with skill in the art to produce sized wet chop or sized dry chopglass fiber strands. These sized glass fiber strands are then availableto be added to an aqueous solution in amounts in the range of about 0.1to about 1 weight percent of the aqueous solution for use as in aqueousglass fiber containing dispersions for paper making.

In the process of the present invention, the desired part per millionamount of the blend of the dispersing agent and defoaming agent is addedto the aqueous solution with agitation, and the desired amount, betweenabout 0.1 to about 1 weight percent of the aqueous solution, of around1/2 inch chopped glass fiber strands, either sized or unsized is addedto the aqueous solution.

Generally the length of the chopped glass fiber strands vary from about1/32 of an inch to about 2 inches and more particularly the averagelength varies from about 1/8 of an inch to about 2 inches. When theaverage length of the glass fiber strands is less than 1/2 of an inch,the amount of glass fibers added to the aqueous solution is preferablyin the upper portion of the range and higher. When the average length ofglass fiber strand is more than 1/2 of an inch, the amount used ispreferably in the lower portion of the range and lower as the averagelength approaches 2 inches. Whenever the chopped glass fiber strands areadded to the aqueous solution it is with the use of agitation. After thechopped glass fiber strands have been added to the aqueous solutioncontaining the blend the aqueous solution is agitated for a period oftime to produce the dispersion containing glass fibers for use in papermaking.

PREFERRED EMBODIMENT

It is the preferred embodiment of the present invention to use thedispersing agent which is a diethyl sulfate quaternary of an alkyl aminooleylamide in a blend with the low-silicon, water dispersible, mineraloil-colloidal silica, liquid defoaming agent available as Nopco 319R.The blend is preferably added to the aqueous solution to which thechopped glass fiber strands are to be added. In the blend, it ispreferred to have an amount of around 90 weight percent of the blend ofthe dispersing agent and around 10 weight percent of the blend of thedefoaming agent. In the preferred process of adding the blend to theaqueous solution, the amount of blend added is preferably about 50 toabout 70 ppm of the aqueous solution to which the glass fibers are to beadded. The aqueous solution with the blend is agitated and chopped glassfiber strands having average filament diameters around 5 to about 17microns in around half-inch lengths are added to the agitating aqueoussolution. It is preferred that the chopped glass fiber strands do notcontain a sizing composition if the filament diameter is around 13microns. The amount of glass fiber strands added to the aqueous solutionis preferably around 0.5 weight percent of the aqueous solution. Theglass fiber strands are added to the aqueous solution with agitation toproduce an aqueous dispersion of glass fibers that can be used in papermaking.

The invention is further elucidated in a non limiting fashion by thefollowing examples.

EXAMPLE I

There was added to 1514 kg of water 200 milliliters of a blend ofdiethyl sulfate quaternary of an alkyl amino oleylamide Nopco 2173B and10 percent of the defoaming agent Nopco 319R. In addition, there wasadded 360 grams of the viscosity building agent Natrasol HR (hydroxyethyl cellulose). With agitation, there was added 20 pounds (9.1 kg) of1/8 inch chopped glass fiber strands composed of filiments having adiameter of around 15 to 16 microns. The aqueous solution containing theglass fiber strands was agitated and produced a good dispersion with lowfoam.

EXAMPLE II

A glass fiber-containing aqueous dispersion with low foam was producedby adding 363 grams of the viscosity building agent hydroxy ethylcellulose and 120 milliliters of a blend of the dispersing agent anddefoaming agent. The dispersing agent was the diethyl sulfatequarternary of an alkyl amino oleylamide which was present in 90 weightpercent of the blend. The antifoaming agent was the water dispersiblelow silicone mineral oil, colloidal silica defoaming agent known asNopco 319R which was present in the blend in an amount of 10 weightpercent of the blend. With agitation there was added 0.5 weight percentof 1/8 inch chopped glass fiber strands, where the fibers in the strandshad a filament diameter of around 6 microns. The strands also containeda starch-lubricant composition. Any conventional starch can be used inthe composition, even the cationic starches. After agitation for aperiod of time, the aqueous dispersion of glass fibers was uniform andhad low foam content.

EXAMPLE III

A similar aqueous dispersion having glass fiber strands was prepared asin Example II, except that the filament diameter of the fibers in thechopped glass fiber strands was around 9.5 microns and the length of thechopped glass fiber was around 1/2 inch. This produced a fairly gooddispersion formation with low foam.

EXAMPLE IV

An aqueous dispersion of chopped glass fibers was prepared using 25pounds (11.3 kg) of water. To this amount of water there was added 1gram of a blend of diethyl sulfate quaternary of an alkyl aminooleylamide, Nopco 2173B material and the water dispersible, low silicon,mineral oil, colloidal silica defoaming agent 319R. In the blend, therewas 75 weight percent of the diethyl sulfate quaternary of an aminooleylamide and 25 weight percent of the defoamer. With agitation, therewas added to the aqueous solution containing the blend 30 grams of 1/2inch chopped glass fiber strands, where the fibers had a filamentdiameter of around 15 to 16 microns. The dispersion was fair, withmedium formation on the agitation and medium roping.

EXAMPLE V

Another aqueous dispersion of chopped glass fiber strands was preparedin the same manner as Example IV except for the amount of the dialkylsulfate quaternary of an alkyl amino fatty acid amide and defoamerpresent in the blend. In this example 60 weight percent of the 1 gramwas the quaternary of the fatty acid and 40 weight was the defoamer. Thedispersion produced was fair with medium formation of glass fibers onthe impeller of the agitator and medium roping (stringy agglomeration)and no clumping.

EXAMPLE VI

An aqueous dispersion of chopped glass fiber strands was prepared as inExample V except a different blend was added to the water before theaddition of the chopped glass fiber strands. The blend was composed of:

10 drops of ammonium hydroxide but any suitable base can be used

2.7 grams of Natrasol 250 HR hydroxy methyl cellulose thickening agent.

These components were stirred with the water until they were dissolved;then there was added:

1.5 ml of the blend of Example V.

The dispersion produced was good with only light roping and clumping atthe pH of 8.65 for the water and modified blend.

ILLUSTRATIVE EXAMPLE I

An aqueous dispersion of glass fibers was prepared in the same manner asExample V except instead of adding the blend to the water only thediethyl sulfate quaternary of an alkyl amino fatty acid amide was added.The amount of the amide added was 1 gram. The aqueous dispersionproduced was very good but had too much foam to be used properly inpapermaking.

ILLUSTRATIVE EXAMPLE II

An aqueous dispersion of glass fibers was prepared with 25 pounds (11.3kg) of water, 1 gram of a cationic material and defoamer, and 30 gramsof chopped glass fiber strands having a starch-polymer-oil size and afilament diameter of the fibers in the strands of 15 to 16 microns and a1/2 inch average filament length. The nitrogen-containing cationicmaterial was a blend of alkyl dimethyl benzyl ammonium, chlorides. Thedefoamer was a clear yellow liquid that was silicone-free with 100percent activity that formed a stable white emulsion in water at 25° C.at 10 percent solution, that has a pH of 6.5 for a 2 percent solution at25° C. and is available from Diamond Shamrock Chemical Company under thetrade designation 419A.

The aqueous dispersion of glass fibers was a good dispersion withoutformation on the impeller of the agitator, but the dispersion had agreat deal of foam. The defoamer had no effect on the foam or thedispersion.

The foregoing has described a blend of a dispersing agent selected fromalkyl sulfate quaternary of an alkyl amino fatty acide amine or amidederivative and a water dispersible, liquid mineral oil, inorganic silicadefoaming agent. The blend is useful in producing aqueous dispersionshaving glass fibers that are uniform and have a low foam content. Theblend can be used as an additive to an aqueous solution before theaddition of the chopped glass fiber strands or as a component of asizing composition for treating glass fiber strands. The foregoing hasalso described the process of adding the blend to the aqueous solutionand then adding the chopped glass fiber strands to produce the uniformlow foam aqueous dispersion of glass fibers.

I claim:
 1. Glass fibers having filament diameters larger than around 13microns that are readily dispersible in aqueous solutions having thereonan aqueous sizing composition, comprising:a. about 0.1 to about 50weight percent of a blend of alkyl sulfate quaternary of an alkyl aminofatty acid amine or amide and a liquid mineral oil-inorganic silicadefoaming agent made water dispersible with a compatible surfactant,where the amount of the quaternary material is in the range of about 50to about 95 weight percent of the blend and the amount of the defoamingagent is around 5 to about 50 weight percent of the blend; b. a glassfiber lubricant; and c. water.
 2. Glass fibers of claim 1 havingfilament diameters less than 13 microns to produce chopped glass fibersthat are more readily dispersible in aqueous solution, that in additionhave present a film former.
 3. Glass fibers of claim 1 or 2 whereinthere is present a silane coupling agent.
 4. Glass fibers of claim 1 or2 wherein there is present a cationic lubricant.
 5. Glass fibers ofclaim 1 or 2 having present a thickening or viscosity building agent. 6.Dried glass fibers of claims 1 or
 2. 7. Glass fibers of claims 1 or 2,wherein the blend of quaternary material and defoaming agent has about 5to about 95 weight percent of the blend as the quaternary material andabout 5 to about 25 weight percent of the blend as the defoaming agent.8. Glass fibers of claim 1 or 2 wherein the dispersing agent is diethylsulfate quaternary of an alkyl amino oleylamide.
 9. Glass fibers ofclaim 1 wherein the defoaming agent is one exhibiting the infraredspectrum of FIG.
 2. 10. Glass fibers of claim 1 wherein the blend of thequaternary material and defoaming agent is one exhibiting the infraredspectrum of FIG.
 1. 11. Glass fibers of claim 5, wherein the thickeningor viscosity building agent is selected from the group consisting ofcarboxy methyl cellulose and soluble salts thereof, carboxy methylhydroxy ethyl cellulose, and soluble salts thereof, and hydroxy ethylcellulose and substituted and unsubstituted hydroxy ethyl cellulose andmixtures thereof.
 12. Glass fibers of claim 2, wherein the film formeris a starch.
 13. Glass fibers of claims 1 or 2, wherein the defoamingagent comprised of the liquid mineral oil-inorganic silica made waterdispersible with a nonionic surfactant has a colloidal silica and has anamount of silicone of less than around 0.5 percent.
 14. Glass fibers ofclaim 1 or 2, wherein the compatible surfactant is a nonionicsurfactant.
 15. Glass fibers of claims 1 or 2, wherein the alkyl sulfatequaternary of an alkyl amino fatty acid or amide is diethyl sulfatequaternary of an alkyl amino oleylamide present in an amount of about 75to about 95 weight percent of the composition when the defoaming agentis present in an amount in the range of about 5 to about 25 weightpercent of the blend.